Silver(i) dithiocarboxylate complexes – clustering and aggregation

Abstract

The neutral silver(I) dithiocarboxylate complexes silver(I) dithioacetate, silver(I) pentafluorodithiobenzoate, silver(I) 2,4,6-trimethyldithiobenzoate, silver(I) 2,4,6-tri-iso-propyldithiobenzoate and silver(I) 2,6-dimesityl-dithiobenzoate were synthesized and characterized by IR spectroscopy, elemental analyses and single crystal X-ray diffraction. All complexes form primarily dinuclear units with eight-membered rings [Ag₂S₄C₂], which in turn aggregate by argentophilic interactions and additional Ag⋯S contacts in their crystal structures. The molecular structures and shapes of aggregation in the solid state are presented and discussed. The layer-like and chain-like aggregates as well as the [Ag] clusters formed are compared with the (almost) analogous gold(I) complexes.